CN111167264A - Tail gas treatment method for polyphenyl ether production device - Google Patents

Tail gas treatment method for polyphenyl ether production device Download PDF

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Publication number
CN111167264A
CN111167264A CN202010100463.0A CN202010100463A CN111167264A CN 111167264 A CN111167264 A CN 111167264A CN 202010100463 A CN202010100463 A CN 202010100463A CN 111167264 A CN111167264 A CN 111167264A
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absorption
tower
tail gas
methanol
concentration
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CN202010100463.0A
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Inventor
衷晟
张洪波
孙长久
李勇
贾喜森
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Dalian Zhongmu Chemical Co Ltd
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Dalian Zhongmu Chemical Co Ltd
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Priority to CN202010100463.0A priority Critical patent/CN111167264A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1487—Removing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1406—Multiple stage absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1412—Controlling the absorption process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1418—Recovery of products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/103—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2021—Methanol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention provides a method for treating tail gas generated by a polyphenyl ether production device by adopting a spray absorption mode so as to enable the tail gas to reach the emission standard. The process is simple, the device operation cost is low, new waste cannot be generated, and the absorbed solution can be recycled.

Description

Tail gas treatment method for polyphenyl ether production device
Technical Field
The invention relates to a method for treating tail gas of a polyphenyl ether production device, in particular to a method for treating tail gas generated by the polyphenyl ether production device by adopting a spraying absorption mode so as to enable the tail gas to reach the emission standard.
Background
Polyphenylene Oxide (PPO) is an excellent thermoplastic, one of five major engineering plastics. Polyphenylene oxide is superior to polycarbonate, polyamide and polyoxymethylene in certain mechanical properties, is a mechanical substitute for nonferrous metals, is used electrically as a coil bobbin, an insulating support, a housing of a television, etc., is used in chemical engineering as a corrosion-resistant pump blade, a pipe, a valve, etc., is used in the medical industry as a part for surgical operations, is used in an automobile as a housing and a part, and is also used in office machines, communication equipment, etc. At present, the synthesis process of polyphenylene ether adopts an oxidative polymerization method of 2, 6-xylenol in an organic solution.
The production of polyphenyl ether mainly comprises steps of oxidative polymerization, filtering and washing, product drying, solvent recovery and the like, wherein in the production process, discharged waste gas of a device is mainly noncondensable gas and rectified noncondensable gas generated by container replacement or respiration, the noncondensable gas mainly contains pollutants such as methanol, toluene, amine, 2, 6-xylenol and the like, and the pollutants are harmful substances to the environment and human bodies and can be discharged into the atmosphere after being treated. At present, the main methods for treating the tail gas comprise cryogenic recovery, alkali spray absorption, activated carbon adsorption, UV (ultraviolet) photolysis, incineration and the like, and one or a combination of several methods is usually used in practical application. However, these methods have drawbacks or disadvantages, such as: the methanol in the methanol is difficult to be removed by cryogenic recovery; although the methanol and the volatile phenol can be absorbed by the alkali spraying absorption, the anisole cannot be absorbed, and new alkaline wastewater is generated and needs to be additionally treated; the adsorption efficiency of the activated carbon is not high, the activated carbon needs to be replaced frequently, and in addition, the replaced activated carbon is also treated as hazardous waste; the actual effect of UV photolysis is not ideal, and the tail gas treated by the UV photolysis method alone is difficult to reach the standard; the mode that tail gas is sent into burning furnace and is burnt is a method that can thoroughly remove organic matter in the tail gas, but not only need consume a large amount of natural gas, and the burning of these natural gases also can produce waste gas simultaneously, has increased the total emission of device waste gas.
Disclosure of Invention
Aiming at the defects of the tail gas treatment method, the invention provides a simpler, environment-friendly and recyclable treatment scheme.
The technical scheme adopted by the invention is as follows:
noncondensable tail gas generated by a polyphenyl ether production device is absorbed in a mode of connecting two stages of spraying absorption towers in series, first-stage absorption liquid is methanol and is used for absorbing various organic substances in the tail gas, such as toluene, amine and volatile phenol, and the absorbed methanol is returned to a polyphenyl ether synthesis system to be used as a raw material; the tail gas after being absorbed by the methanol basically does not contain organic substances such as toluene, amine, volatile phenols and the like except the methanol, the tail gas is subjected to secondary absorption, the methanol in the tail gas is further absorbed by adopting water as an absorption liquid, the absorbed aqueous solution returns to a rectifying tower in a production device for methanol recovery, and the rectified water can be recycled as the methanol absorption liquid of a spray absorption tower. The absorption operation is finished under certain temperature and pressure in the spray absorption tower.
The tail gas in the technical scheme comprises the following components: nitrogen, water, methanol and methanolBenzene, amine, 2, 6-xylenol and the like, wherein the concentration of methanol is 10000-50000 mg/m3The concentration of toluene is 1000-5000 mg/m3The amine concentration is 500-3000, the 2, 6-xylenol concentration is 10-100 mg/m3。
In the technical scheme, the tail gas absorption equipment is a spray absorption tower, liquid enters the absorption tower from the top of the tower and is discharged from the tower kettle, and gas enters the absorption tower from the lower part of the tower and is discharged from the top of the tower.
In the technical scheme, the tail gas absorption operation can adopt liquid circulation absorption or brand new fresh liquid absorption, and absorption liquid does not circulate and flow back. When the cyclic absorption operation is adopted, the reflux ratio can be adjusted according to the requirement of tail gas indexes.
In the technical scheme, the tail gas absorption operation temperature is 0-50 ℃, and preferably 10-30 ℃.
In the technical scheme, the tail gas absorption operation pressure can be negative pressure or normal pressure or positive pressure, and preferably normal pressure or slight positive pressure.
The invention has the advantages that: the process is simple, the device operation cost is low, new waste cannot be generated, and the absorbed solution can be recycled.
Detailed Description
Example 1
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration was 19000mg/m3The toluene concentration was 1800mg/m3Amine concentration of 800mg/m3The concentration of 2, 6-xylenol is 47mg/m368 m of exhaust gas flow3And h, introducing the methanol from the lower part of a spray absorption tower, pumping the primary absorption liquid with the flow of 50kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 10 ℃, the operation pressure of the tower is normal pressure, the absorbed methanol is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 1: 1, the rest part is sent into a methanol intermediate tank to be used as a raw material, tail gas is absorbed and then comes out from a first-stage absorption tower, and is introduced from the lower part of a second-stage spraying absorption tower, the flow of second-stage absorption liquid water is 50kg/h, the second-stage absorption liquid water is pumped into the absorption tower from the top of the tower, the temperature of feed water is 10 ℃, the operating pressure of the tower is normal pressure, the absorbed water is pumped up from the bottom of the tower through a pump, and the part of the absorbed water is used as reflux: 1The rest part is sent to a methanol removing tower to recover the methanol, the tail gas is discharged into the atmosphere from an exhaust funnel after being absorbed, and the concentration of the methanol is 6mg/m after analysis3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.
Example 2
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration is 31000mg/m3Toluene concentration of 2700mg/m3Amine concentration 1100mg/m3The concentration of the 2, 6-xylenol is 76mg/m3Exhaust gas flow of 65m3Introducing methanol from the lower part of a spray absorption tower, pumping the primary absorption liquid with the flow of 70kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 10 ℃, the operation pressure of the tower is normal pressure, the absorbed methanol is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 0.5: 1, the rest part is sent into a methanol intermediate tank to be used as a raw material, tail gas is absorbed and then comes out from a first-stage absorption tower, and is introduced from the lower part of a second-stage spraying absorption tower, the flow of second-stage absorption liquid water is 50kg/h, the second-stage absorption liquid water is pumped into the absorption tower from the top of the tower, the temperature of feed water is 10 ℃, the operating pressure of the tower is normal pressure, the absorbed water is pumped up from the bottom of the tower through a pump, and the part of the absorbed water is used as reflux: 1, the rest part is sent to a methanol removing tower to recycle the methanol, the tail gas is discharged into the atmosphere from an exhaust funnel after being absorbed, and the concentration of the methanol is 7mg/m after analysis3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.
Example 3
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration is 42000mg/m3Toluene concentration is 3500mg/m3The amine concentration is 2100mg/m3The concentration of 2, 6-xylenol is 56mg/m3Exhaust gas flow rate of 63m3Introducing methanol from the lower part of a spray absorption tower, pumping primary absorption liquid with the flow of 100kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 10 ℃, the operation pressure of the tower is normal pressure, the absorbed methanol is pumped from the bottom of the tower to be boosted without refluxing, the methanol is completely sent to a methanol intermediate tank to be used as a raw material, and tail gas is dischargedThe absorption liquid is discharged from a first-stage absorption tower after absorption and is introduced from the lower part of a second-stage spray absorption tower, the flow of second-stage absorption liquid water is 60kg/h, the absorption liquid is pumped into the absorption tower from the top of the tower, the temperature of feed water is 10 ℃, the operation pressure of the tower is normal pressure, the absorbed water is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 0.5: 1, the rest part is sent to a methanol removing tower to recycle the methanol, the tail gas is discharged into the atmosphere from an exhaust funnel after being absorbed, and the concentration of the methanol is 5mg/m after analysis3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.
Example 4
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration is 25000mg/m3Toluene concentration of 2900mg/m3The amine concentration is 1800mg/m3The concentration of 2, 6-xylenol is 69mg/m3Exhaust gas flow of 66m3Introducing methanol from the lower part of a spray absorption tower, pumping the primary absorption liquid with the flow of 80kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 15 ℃, the operation pressure of the tower is normal pressure, the absorbed methanol is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 0.3: 1, the rest part is sent into a methanol intermediate tank to be used as a raw material, tail gas is absorbed and then comes out from a first-stage absorption tower, and is introduced from the lower part of a second-stage spraying absorption tower, the flow of second-stage absorption liquid water is 60kg/h, the second-stage absorption liquid water is pumped into the absorption tower from the top of the tower, the temperature of feed water is 20 ℃, the operating pressure of the tower is normal pressure, the absorbed water is pumped up from the bottom of the tower by a pump, and the reflux ratio is 0.6: 1, the rest part is sent to a methanol removing tower to recycle the methanol, the tail gas is discharged into the atmosphere from an exhaust funnel after being absorbed, and the concentration of the methanol is 11 mg/m after analysis3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.
Example 5
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration is 42000mg/m3The toluene concentration was 4500mg/m3The amine concentration was 2900mg/m3The concentration of the 2, 6-xylenol is 88mg/m3Tail gas streamAmount 65m3Introducing methanol from the lower part of a spray absorption tower, pumping primary absorption liquid methanol with the flow rate of 100kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 15 ℃, the operation pressure of the tower is normal pressure, the absorbed methanol is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 0.5: 1, the rest part is sent into a methanol intermediate tank to be used as a raw material, tail gas is absorbed and then comes out from a first-stage absorption tower, and is introduced from the lower part of a second-stage spraying absorption tower, the flow of second-stage absorption liquid water is 80kg/h, the second-stage absorption liquid water is pumped into the absorption tower from the top of the tower, the temperature of feed water is 10 ℃, the operating pressure of the tower is normal pressure, the absorbed water is boosted by a pump from the bottom of the tower and does not reflux, all the water is sent into a methanol removing tower to recover methanol, the tail gas is absorbed and then is discharged into the atmosphere from an exhaust funnel3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.
Example 6
The concentration of pollutants in the tail gas of the device is as follows: the methanol concentration is 31000mg/m3The toluene concentration was 2600mg/m3The amine concentration is 1400mg/m3The concentration of 2, 6-xylenol is 38mg/m3Exhaust gas flow of 64m3And h, introducing the methanol from the lower part of a spray absorption tower, pumping the primary absorption liquid with the flow rate of 60kg/h into the absorption tower from the top of the tower, wherein the temperature of the fed methanol is 10 ℃, the operation pressure of the tower is 50kPa, the absorbed methanol is partially used as reflux liquid of the tower after being boosted by a pump from the bottom of the tower, and the reflux ratio is 0.5: 1, the rest part is sent into a methanol intermediate tank to be used as a raw material, tail gas is absorbed and then comes out from a first-stage absorption tower, and is introduced from the lower part of a second-stage spraying absorption tower, the flow of second-stage absorption liquid water is 50kg/h, the tail gas is pumped into the absorption tower from the top of the tower, the temperature of feed water is 10 ℃, the operating pressure of the tower is 50kPa, the absorbed water is pumped from the bottom of the tower to be boosted by a pump, and the reflux ratio is 1: 1, the rest part is sent to a methanol removing tower to recycle the methanol, the tail gas is discharged into the atmosphere from an exhaust funnel after being absorbed, and the concentration of the methanol is 3 mg/m after analysis3Concentration of toluene<1 mg/m3Concentration of amine<1 mg/m3Concentration of 2, 6-xylenol<1 mg/m3And completely reaches the emission standard.Completely reaches the discharge standard.
The above embodiments are all specific embodiments of the present invention, and the present invention is not limited by the above embodiments. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention, and it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

Claims (6)

1. A tail gas treatment method of a polyphenyl ether production device is characterized by comprising the following steps: the tail gas of the device is absorbed in two stages in series, the first stage absorption liquid is methanol and is used for absorbing various organic substances in the tail gas, and the methanol returns to the synthesis system after absorption and is used as a raw material; the second-stage absorption liquid is water, the methanol in the tail gas after the first-stage absorption is absorbed, and the absorbed water returns to the rectifying tower for methanol recovery; the absorption operation is completed in an absorption tower under certain temperature and pressure.
2. The exhaust gas composition of claim 1 comprising: nitrogen, water, methanol, toluene, amine, 2, 6-xylenol and the like, wherein the concentration of the methanol is 10000-50000 mg/m3The concentration of toluene is 1000-5000 mg/m3The amine concentration is 500-3000, the 2, 6-xylenol concentration is 10-100 mg/m3。
3. The tail gas absorption equipment according to claim 1 is a spray absorption tower, liquid enters the absorption tower from the top of the tower and is discharged from the bottom of the tower, and gas enters the absorption tower from the lower part of the tower and is discharged from the top of the tower.
4. The tail gas absorption operation of claim 1 can be liquid circulation absorption or fresh liquid absorption, and the absorption liquid does not circulate and flow back.
5. The tail gas absorption operation temperature of the method according to claim 1 is 0-50 ℃, preferably 10-30 ℃.
6. The tail gas absorption operating pressure according to claim 1 may be a negative pressure or an atmospheric or positive pressure, preferably an atmospheric or a slight positive pressure.
CN202010100463.0A 2020-02-18 2020-02-18 Tail gas treatment method for polyphenyl ether production device Pending CN111167264A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5772734A (en) * 1997-01-24 1998-06-30 Membrane Technology And Research, Inc. Membrane hybrid process for treating low-organic-concentration gas streams
CN105056706A (en) * 2015-08-19 2015-11-18 常州大学 Methanol waste gas recycling system based on secondary absorption
CN105688597A (en) * 2016-03-31 2016-06-22 四川天采科技有限责任公司 Full-temperature-process pressure swing adsorption method for recycling hydrocarbons from low-temperature methyl alcohol washing tail gas
CN109012037A (en) * 2018-08-08 2018-12-18 东华工程科技股份有限公司 A kind of purification separation system of polyphenylene oxide polymerization tail gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5772734A (en) * 1997-01-24 1998-06-30 Membrane Technology And Research, Inc. Membrane hybrid process for treating low-organic-concentration gas streams
CN105056706A (en) * 2015-08-19 2015-11-18 常州大学 Methanol waste gas recycling system based on secondary absorption
CN105688597A (en) * 2016-03-31 2016-06-22 四川天采科技有限责任公司 Full-temperature-process pressure swing adsorption method for recycling hydrocarbons from low-temperature methyl alcohol washing tail gas
CN109012037A (en) * 2018-08-08 2018-12-18 东华工程科技股份有限公司 A kind of purification separation system of polyphenylene oxide polymerization tail gas

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Application publication date: 20200519